Oil-soluble phospho-halo-containing ethylene/propylene copolymers



3,290,276 OIL-SOLUBLE PHGSIHG-HALQ-CONTAINING ETHYLENE/PRGPYLENECOPOLYMERS William S. Anderson, Oakland, Calif., assignor to Shell OilCompany, a corporation of Delaware No Drawing. Original application Dec.21, 1959, Ser. No. 860,716, new PatentNo. 3,105,819. Divided and thisapplication May 3, 1963, Ser. No. 277,705

3 Claims. (Cl. 260--88.2)

This patent application is a division of c-opending case, Serial No.860,716, filed December 21, 1959, and is now U.S. Patent 3,105,819.

This invention relates to a new and novel class of polymers. Moreparticularly the invention is directed to multifunctional polymerscontaining a plurality of phosphor-us units attached to a longhydrocarbon back bone chain.

In the field of lubrication non-ash forming polymeric detergent extremepressure additives are particularly desirable although copolymers ofthis invention have many other applications as will be shownhereinbelow.

It has been discovered that polymers which meet this requirement areoil-soluble copolymers of the present invention which arepolyphosphonated copolymers of ethylone and a lower monoalkyl ethylenesuch as copolymers of ethylene and propylene or ethylene and bute-n-e-lor mixtures thereof. In copolymers of this invention the ethyleneprecurser comprises at least 20% of the total mixture at least 10% andpreferably 15-40% of the phosphonated copolymer product. Thephosphonated copolymer has a plurality of units represented by:

units, normally if present vary from about 2% to about 15% of units (1).Copolymers of this invention range in molecular weight from about 5,000to about 1,000,000, preferably between about 100,000 and about 500,000.The symbols in the above formulas are: R is a C alkyl radical,preferably a CH radical, the Xs can be --YR' and where Y is oxygen orsulfur and R is -a hydrocarbyl radical, such as C prefer-ably C alkyl,cycloalkyl, aralkyl radical or a cation such as amine, e.g. C alkylamine, polyamine, e.g. an alkylene diamine, a heterocyclic amine, e.g.alkyl substituted pyridine, etc.

The phosphonated copolymers of the present invention are prepared byreacting ethylene and a lower monoalkyl ethylene such as propylene,butene-l and the like to form copolymers such as ethylene/propylenecopolymer made by the procedures and techniques described in Irishpatent application 695/56 and treating said copolymer with phosphoruschloride under oxidizing conditions, such as by blowing air or oxygenthrough the reaction mixture under controlled temperature conditions. Inessence the intermediate product, that is the elastomeric copolymer, isproduced by polymerizing a mixture of ethylene and propylene in thepresence of an inert hydrocarbon solvent with a catalyst of the Zieglertype which essentially is a reaction product of a metallo-alkyl compoundof Groups I, II or III and a metal halide such as vanadium chloride orvanadium oxychloride. The ratio of ethylene and propylene monomers thatis maintained during the polymerization will vary depending on theproportion of the United States Patent 0 elastomer.

Patented Dec. 6, 1966 respective monomers desired in the finalelastomer. In the preferred embodiments the elastomer may contain fromabout 20 mole percent of about mole percent, preferably 30-80 molepercent of ethylene units in the copolymer and still be useful in theformation of the Because the monomers do not polymerize at the samerate, i.e. ethylene polymerizes faster than propylene, the ratio of thestarting mixture of monomer is not the same as that desired in the finalproduct and this is one of the major considerations in selecting thestarting monomer ratios to give a particular final product. Otherconsiderations are the choice of catalyst components and theirrespective proportions and the polymerization conditions. By way ofillustration, Table I indicates variations of ethylene units in thefinal elastomer as the ratio of ethylene to propylene in the startingmonomer mixture is varied. For this table, polymerizations wereconducted at 45-65 C. in n-heptane solvent and the catalyst was thereaction product of-trihexyl-aluminum and vandium oxychloride in a moleratio of 3.011.

Table I Mole percent Ethylene in Feed Gases Other suitable alkylaluminum compounds as the catalyst component include trioctyl aluminum,trinonyl aluminum, tridecyl aluminum, triiso-butyl aluminum, and others.Preferably the alkyl radicals of the trialkyl aluminum have more than 4carbon atoms but not more than 16 carbon atoms. For economic reasons,the number of carbon atoms in the alkyl radicals preferably range from 4to 10. The ratio of the aluminum compounds to the vanadium oxychlorideor vanadium tetrachloride may vary widely but preferably the aluminum tovanadium mole ratio is greater than 2. The catalyst is simply preparedby mixing and reacting the catalyst components in a hydrocarbon solventwhereupon there is formed a reaction product which is the catalyst.

The final phosphorus-containing polymeric product of this invention isobtained by reacting an elastomeric ethylene-propylene copolymer of thetype described above with phosphorus trichloride, phosphorusoxychloride, phosphor-us tribromide, etc. in an inert solvent underoxidizing conditions, such as by blowing air or oxygen through themixture at controlled temperatures of from about 0 to 60 C., preferablyat 1035 C. The resulting polyph-osphonyl halide-containing copolymer canbe hydro lyzed to form the polyphosphonic acid and the acid esterifiedor converted into salts by suitable means. The time required forcompleting the reaction depends upon the number of units (1) which aredesired to be provided in the copolymer as well as the ratio of thereactants and the reaction temperature. In general, the time required tocomplete the reaction may vary from 2 to 48 hours or more.

The following examples are given as illustrative of the presentinvention.

EXAMPLE I To a mixture of 222 grams of Ziegler type copolymer of 50%ethylene and 50% propylene having an intrinsic viscosity of 5.5 dl./ g.in 2.8 liters of benzene was added dropwise 365 grams of PCI, over aperiod of 3 hours while simultaneously bubbling oxygen through themixture and controlling the temperature of the reaction at 1234 C. byice cooling the reaction vessel. About 550 ml. of methanol was thenslowly added, and the resulting HCI swept out with nitrogen. To theproduct about 1 gram of a phenolic anti-oxidant [2,2-methylenebis(4-methyl- 6-tert.butylphenol)] was added as well as 625 ml. ofpyridine and the entire mixture was cooled and allowed to stand for 48hours. The pyridine salts were filtered off and the polymer precipitatedby adding methanol and then reprecipitated three times from benzene intomethanol. On analysis the resulting mixed methyl phosphonatephosphonylchloride containing ethylene/propylene copolymer contained 2.41%phosphorus and 0.983% chloride corresponding to 14% of theethylene/propylene copolymer units containing the phosphono group.

Following the above procedure, the following phosphono-modifiedelastomeric copolymers oat ethylene/propylene having an intrinsicviscosity in the range of l to 10 dl./ g. were prepared:

II. Poly(dibutylphosphonate) of ethylene/propylene copolymer havingintrinsic viscosity of 2 d1./ g.

III. Poly(dihexylphosphonate) of ethylene/propylene cpolymer havingintrinsic viscosity of 34 dl./ g.

IV. Poly(dilaurylphosphonate) of ethylene/ propylene copolymer havingintrinsic viscosity of dl./ g.

V. P0ly(stearyl acid phosphonate) of ethylene/ propylene copolymerhaving intrinsic viscosity of 2 dl./ g.

VI. Poly(dicyclohexyl phosphonate-phosphonylchloride) ethylene/butene-lcopolymer having an intrinsic viscosity of 4-6 dl./ g.

The polymeric compounds of this invention are eifective oil additivesimparting to lubricants detergency and wear inhibiting properties. Also,they may be used as ion exchange resins, fire-resistent materials,adhesives, coatings, as insecticidal materials, alone or in conjunctionwith other well known insecticidal agents such as DDT, DDD, aldrin,parathion, Chlorothion and the like. However, polymers of the presentinvention are outstanding for their ability to impart to mineral oil (1)detergency as determined by the Carbon Black Dispersency Test describedin the Journal of Colloid Science, vol. 12, October 1957, No. 5, pages500522; at 100 C. and 5 r.p.m. and (2) anti-wear properties usingOldsmobile Tappet Wear Test Ring under GMMS Test conditions (2500r.p.m., 300 number valve open spring load described in the AMA proposedspecification for evaluation of oils for API Service classification MSpresented at SAE meeting, Atlantic City, New Jersey, June 1958). Theresults are shown in Table II and the compositions tested were asfollows:

Percent Composition A:

Example I additive 2. 1010 neutral mineral oil Essentially balance.Composition B:

Example 11 additive 2.

1010 neutral mineral oil Essentially balance. Composition C:

Example III additive 2 1010 mineral oil a Essentially balance.

Composition D:

Di-2-ethyl hexyl sebacate Essentially balance.

Composition H:

Example I additive 5.. Ucon 50HB660 (polyethylenepropylene glycol havinga SUS viscosity at F. of 660) Essentially balance. Composition 1:

Example I additive 5. Di-2-ethylhexyl sebacate Essentially balance.

Table II GM-MS Test Detergency Composition (deflocculating Av. Av. Cam

ability) lifter B wear,

visual thourating sands of inch (1) 100 Neutral mineral oil 3 X 10 ohms.5 44 (2) (1) 2% Ca petroleum 3.3 X 10 ohms 5 44 sulfonate. ans alkyl 3 X10 ohms 5 44 methacrylate copolymer. (4) Compositions A-I (present 12 X10 ohms 9 0 invention).

10=perfect.

From the test results the superiority of compositions of the presentinvention to oils containing convention detergents (2) or polymers (3)with respect to detergency, cleanliness and wear inhibition is clearlyevidenced. Thus, representative compositions of the present invention(4) is about 4 times as effective as a detergent as are compositions (2)and (3) or a neat oil (1), twice as effective in preventing sludge andmany more times effective as a wear inhibitor than that of compositions(1), (2) or (3).

The polymers of this invention are useful also for providing superiorload-carrying properties in lubricating oils which contain minor amountsof other agents which are non-reactive with the polymer, such assilicone anti-foaming agents, alkylphenol anti-oxidants, polyacrylateester viscosity-index improvers, and the like.

I claim as my invention:

1. An oil-soluble polyphosphonate of ethylene/propylene copolymer, thephosphonate units in the copolymer being represented by RO/ \OR where Ris an alkyl selected from the group consisting of lauryl and stearylradicals and the number of such units comprise from 10% to 40% of theethylene/propylene copolymer, said copolymer having a molecular weightof from 5000 to 1,000,000.

2. The copolymer of claim 1 wherein R is lauryl and the mole percent ofethylene is 30-80 mole percent and the balance is propylene.

3. The copolymer of claim 1 wherein R is stearyl and the mole percent ofethylene is 30-80 mole percent and the balance is propylene.

References Cited by the Examiner UNITED STATES PATENTS 3,008,939 11/1961Schroeder et al. 260-94.9 3,023,180 2/1962 Canterino et al. 260-949JOSEPH L. SCHOFER, Primary Examiner. L. E. DELMAN, Assistant Examiner.

1. AN OIL-SOLUBLE POLYPHOSPHONATE OF ETHYLENE/PROPYLENE COPOLYMER, THEPHOSPHONATE UNITS IN THE COPOLYMER BEING REPRESENTED BY